Chiral amine-squaramide compound based on spirobiindane skeleton, preparation method and use thereof

Abstract

A chiral amine-squaramide compound based on a spirobiindane skeleton, a preparation method and use thereof provided. The chiral amine-squaramide is an enantiomeric compound having the general formula (I) and is useful for asymmetric catalytic organic reactions with good catalytic activity and enantioselectivity. The chiral amine-squaramide compound is obtained by preparation of compound of formula (I) through addition of a compound of formula (II) with squaric acid ester. The synthetic reaction route is simple, and it is easy for large-scale application. The novel chiral amine-squaramide organocatalyst has economic utility and promising industrial applications.

What is claimed is: 
     
         1 . A chiral amine-squaramide compound of formula (I) based on a spirobiindane skeleton: 
       
         
           
           
               
               
           
         
         wherein, 
         X is H, CH 3;    
         R 1 , R 6 , R 3 , R 4  are H; 
         R 2 , R 5  are H or CH 3 ; 
         a moiety 
       
       
         
           
           
               
               
           
         
         R 9  phenyl, substituted phenyl, phenylmethylene or phenylethylidene, the substituted phenyl is 1-5 membered replaced with substituents selected from F, CI, Br, I, NO 2 , CN, C 1-4  alkyl, C 1-4  perfluoroalkyl, C 1-4  alkoxy, C 1-4  perfluoroalkoxy, 
         an enantiomer thereof, a racemate thereof or a diastereomer thereof. 
       
     
     
         2 . The chiral amine-squaramide compound of formula (I), an enantiomer thereof, a racemate thereof or a diastereomer thereof according to  claim 1 , wherein the chiral amine-squaramide of formula (I) is: 
       
         
           
           
               
               
           
         
       
     
     
         3 . A method for preparing the chiral amine-squaramide compound of formula (I) according to  claim 1 , comprising the following step: allowing a compound of formula (II) and a compound of formula (II-e) to have an addition reaction in an organic solvent to obtain a compound of formula (I): 
       
         
           
           
               
               
           
         
         wherein X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  and R 9  are as defined in  claim 1 . 
       
     
     
         4 . Use of the chiral amine-squaramide compound of formula (I) based on a spirobiindane skeleton, an enantiomer thereof, a racemate thereof or a diastereomer thereof according to  claim 1 , wherein the chiral amine-squaramide compound of formula (I) based on a spirobiindane skeleton, an enantiomer thereof, a racemate thereof is used in an asymmetrically catalyzed addition reaction. 
     
     
         5 . The use according to  claim 4 , wherein the asymmetrically catalyzed addition reaction is an asymmetrically catalyzed conjugate addition reaction of a 3-trifluoroethylidene indolinone derivative and a pyrazol-3-one.